Cleavage of the indium(III) octaethyloxophlorin dimer, {In(III)(OEPO)}2, with Lewis bases. Importance of outer-sphere hydrogen bonding in adduct structures.
Splitting of the oxygen-bridged dimer {In(III)(OEPO)}(2) [where (OEPO)(3-) is the trianion of octaethyloxophlorin] by potential axial ligands has been examined and compared to results obtained previously for the cleavage of {Fe(III)(OEPO)}(2). Treatment of {In(III)(OEPO)}(2) with an excess of imidazole (im) produced the crystalline complex {(im)(2)In(III)(OEPO...im)}(2).(im)(2)In(III)(OEPO).2Cl(2)C(6)H(4). This solid contains two different (im)(2)In(III)(OEPO) units that are bridged through hydrogen bonding by an uncoordinated imidazole. Treatment of {In(III)(OEPO)}(2) with an excess of pyridine (py) produced (py)(2)In(III)(OEPO), which is isostructural with (py)(2)Fe(III)(OEPO). Although {Fe(III)(OEPO)}(2) reacted with xylyl isocyanide (xylylNC) to form the novel free-radical complex (2,6-xylylNC)(2)Fe(II)(OEPO(*)) [where (OEPO(*))(2-) is the radical dianion of octaethyloxophlorin], {In(III)(OEPO)}(2) was unreactive toward xylyl isocyanide.
Garcia
Thelma Y
TY
Department of Chemistry, University of California, Davis, California 95616, USA.
Olmstead
Marilyn M
MM
Fettinger
James C
JC
Balch
Alan L
AL
D018360:Crystallography, X-Ray; D004583:Electrons; D006860:Hydrogen Bonding; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry
D008024:Ligands; D009942:Organometallic Compounds; D011166:Porphyrins; C539580:indium(III) octaethyloxophlorin dimer